Lubricating oils and fuels containing acylated nitrogen additives

ABSTRACT

COMPOSITIONS OF MATTER PARTICULARLY USEFUL AS LUBRICANT AND FUEL ADDITIVES PREPARED BY REACTING VARIOUS NITROGENCONTAINING REACTANTS WITH A MONO-OR POLYCARBOXYLIC ACID ACYLATING AGENT CONTAINING AT LEAST ABOUT THIRTY ALIPHATIC CARBON ATOMS. THE NITROGEN-CONTAINING REACTANTS ARE CHARACTERIZED BY THE PRESENCE OF AT LEAST ONE N-SUBSTITUENT CORRESPONDING TO   WHERE R IS 1-10 AND R&#39;&#39;&#39;&#39; IS HYDROCARBYLENE OF UP TO 10 CARBON ATOMS. AN EXEMPLARY COMPOSITION IS ONE PREPARED BY REACTING POLYISOBUTENYL SUCCINIC ANHYDRIDE WITH THE REACTION PRODUCT OF N-(HYDROXYETHYL)-ETHYLENE DIAMINE AND ADIPIC ACID.

United States Patent 3,630,904 LUBRICATING OILS AND FUELS CONTAININGACYLATED NITROGEN ADDITIVES Jerry L. Musser and Edward J. Friihauf,Mentor, Ohio, assignors to The Lubrizol Corporation, Wicklilfe, Ohio NoDrawing. Continuation-impart of applications Ser. No. 742,133, July 3,1968, and Ser. No. 851,736, Aug. 18, 1969. This application Nov. 10,1969, Ser. No. 875,580

Int. Cl. C10m 1/20, 1/32; C10l N22 US. Cl. 25251.5 A 30 Claims ABSTRACTOF THE DISCLOSURE Compositions of matter particularly useful aslubricant and fuel additives prepared by reacting variousnitrogencontaining reactants with a monoor polycarboxylic acid acylatingagent containing at least about thirty aliphatic carbon atoms. Thenitrogen-containing reactants are characterized by the presence of atleast one N-substituent corresponding to where r is 1-10 and R" ishydrocarbylene of up to 10 carbon atoms. An exemplary composition is oneprepared by reacting polyisobutenyl succinic anhydride with the reactionproduct of N-(hydroxyethyl)-ethylene diamine and adipic acid.

This is a continuation-in-part application of applicants copendingapplications Ser. No. 742,133, filed July 3, 1968, and Ser. No. 851,736,filed Aug. 18, 1969, both now abandoned.

This application relates to novel compositions of matter and tolubricants and fuels containing these compositions. More specifically,the invention relates to novel, oil-soluble, acylated nitrogencompositions, methods for their preparation, and to lubricants and fuelscontaining the novel acylated nitrogen compositions.

As is Well known, high molecular weight acylated nitrogen compositionshave achieved widespread use as ashless dispersants in lubricants andfuels during the past decade. Generally, these ashless dispersants areprepared by reacting a high molecular Weight monoor polycarboxylic acidacylating agent with a suitable amine or hydroxy compound. Typicalprior-art acylated nitrogen compositions which have utility assludge-dispersing additives in lubricants and fuels are presented indetail in the following US. patents: 3,172,892; 3,219,666; 3,272,746;3,340,281; 3,341,542; 3,361,673; and 3,381,022.

The commercial success of these acylated nitrogen compositions asashless dispersants is conclusive evidence of their effectiveness assludge-dispersants. However, their use has not been entirely free fromproblems. For example, in certain types of automobile engines, it hasbeen found that a sludge forms on metal surfaces in areas of the enginewhere water vapor can condense and which also comes into contact withthe lubricating oil containing one or more of these ashless dispersants.For example, such sludges have been found in the rocker arm covers andoil-fill caps of certain engines, particularly, smaller car engines.Apparently, the breathing systems of these engines are such that theypermit moisture-laden air to come into contact with these metal surfaceswhich are sufliciently cool to permit the condensation of water. Whenthe lubricating oil containing the ashless dispersant comes into contactwith the condensed water, the oil and water apparently form water-in-oilemulsions in the presence of the dispersant. However, it should also benoted at this point that other additives used in lubricating oils3,530,904 Patented Dec. 28, 1971 can also promote the formation of suchwater-in-oil emulsions, for example, some of the commercially usedviscosity index improving agents. It is obviously desirable to eliminateor reduce the amount of emulsion sludge formed 5 in the engine.

It has now been determined that the emulsion-forming tendency of thelubricating oil containing the ashless dispersants can be eliminated orgreatly reduced if the ashless dispersant is prepared from a particularclass of nitrogen-containing compounds Without any substantial adverseeffect on the sludge-dispersing capabilities of the acylated nitrogencomposition. Not only are the novel acylated nitrogen compositions ofthis invention themselves characterized by a reduced tendency to formthe water-in-oil emulsions, their presence in lubricating oils alsoserves to retard the emulsion sludge-forming tendencies of otheradditives in the lubricating oil composition.

In accordance with the foregoing, it is a principal object of thisinvention to provide novel acylated compositions.

V A further object is to provide oil-soluble acylated nitrogencompositions suitable as additives in lubricants and fuels.

An additional object is to provide acylated nitrogen compositionscharacterized by a reduced tendency to promote water-in-oil emulsions.

Still another object is to provide a process for preparing theoil-soluble acylated nitrogen compositions.

Another object is to provide novel post-treated additives for lubricantsand fuels.

A still further object is to provide lubricants and fuels containing theacylated nitrogen compositions of this invention.

These and other objects of this invention are readily achieved byproviding oil-soluble acylated nitrogen compositions produced by theprocess comprising reacting (I) At least one monoor polycarboxylicacylating agent characterized by the presence of at least about thirtyaliphatic carbon atoms, exclusive of carboxyl carbon atoms, with (II) Atleast one nitrogen-containing reactant of the formula IXI (XI! pa an)where:

55 (d) when x is 0:, then Y is where m is 0 or a whole number of l to 8;

(e) when X is R N== then R is R together with Y form a cyclic amidine ofthe formula n" a R! where q is or a whole number of 1 to 8;

(f) when X" is 0: then Z is OM+, halo, lower alkoxy,

or Y as Y is defined when X' is 0:, M+ being the cation of an amine;

(g) when X" is R N= then Z and R are the same as Y and R as thesevariables are defined when X is (h) when X and X are both 0: and Rseparates II II group by two or three carbon atoms, then Y and Z takentogether can be N-RNR-NRR where R is H, hydrocarbyl of up to ten carbonatoms, or

where r is 1 to 10 but at least one R is i O\ per nitrogen-containingreactant; R" is hydrocarbylene of up to ten carbon atoms; (I) and (II)being reacted in amounts such that there is at least one equivalent of(I) to each mole of (II).

Carboxylic acid acylating agents, that is, (1) above, suitable forpreparing the products of the invention are well-known in the art andhave been described in detail, for example, in U.S. Pats. 3,087,936,3,163,603; 3,172,892; 3,189,544; 3,219,666; 3,272,746; 3,288,714;3,306,907; 3,331,776; 3,340,281; 3,341,542; 3,346,354; 3,374,174; and3,381,022. In the interest of brevity, these patents are incorporatedherein for their disclosure of suitable monoand polycarboxylic acidacylating agents which can be used for the preparation of theseproducts.

As disclosed in the foregoing patents, there are several processes forpreparing the acylating agents. Generally, the process involves thereaction of 1) an ethylenically unsaturated carboxylic acid, acidhalide, or anhydride with (2) an ethylenically unsaturated hydrocarboncontaining at least above fifty aliphatic carbon atoms or a chlorinatedhydrocarbon containing at least about fifty aliphatic carbon atoms at atemperature within the range of about 100-300 C. The chlorinatedhydrocarbon or ethylenically unsaturated hydrocarbon reactant can, ofcourse, contain polar substituents, oil-solubilizing pedant groups, andbe unsaturated within the general limitations explained hereinbelow. Itis these hydrocarbon reactants which provides most of the aliphaticcarbon atoms present in the acyl moiety of the final products.

When preparing the carboxylic acid acylating agent according to one ofthese two processes, the carboxylic acid reactant usually corresponds tothe formula where R is characterized by the presence of at least oneethylenically unsaturated carbon-to-carbon covalent bond and n is aninteger from one to six and preferably one to two. The acidic reactantcan also be the corresponding carboxylic acid halide, anhydride, ester,or other equivalent acylating agent and mixtures of one or more ofthese. Ordinarily, the total number of carbon atoms in the acidicreactant will not exceed ten and generally will not exceed six.Preferably the acidic reactant will have at least one ethylenic linkagein an or,fi-p0Sltl0n will respect to at least one carboxyl function.Exemplary acidic reactants are acrylic acid, methacrylic acid, maleicacid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride,citraconic acid, citraconic anhydride, mesaconic acid, glutaconic acid,chloromaleic acid, aeonitic acid, erotonic aid, methylcrotonic acid,sorbic acid, 3-hexenoic acid, 10- decenoic acid, and the like. Due tosuch considerations as economy, availability, reactivity, andperformance of the products, the acid reactants usually employed are theafiunsaturated dicarboxylic acid acylating agents, particularlyu,,B-ethylenically unsaturated dicarboxylic acids and the correspondinganhydrides such as maleic acid, maleic acid anhydride, fumaric acid,etc.

As is apparent from the foregoing discussion, the carboxylic acidacylating agents may contain cyclic and/or aromatic groups. However, theacids are essentially aliphatic in nature and, in most instances, thepreferred acid acylating agents are aliphatic polycarboxylic acids,anhydrides, or halides, usually the chlorides in case of the latter.

The substantially saturated aliphatic hydrocarbon-substituted succinicacids and anhydrides are especially preferred as acylating agents. Thesesuccinic acid acylating agents are readily prepared by reacting maleicanhydride with a high molecular weight olefin or a chlorinatedhydrocarbon such as a chlorinated polyolefin. The reaction involvesmerely heating the two reactants at a temperature of about l00300 C.,preferably, 100200 C. The product from such a reaction is a substitutedsuccinic anhydride where the substituent is derived from the olefin orchlorinated hydrocarbon as described in the above cited patents. Theproduct may be hydrogenated to remove all or a portion of anyethylenically unsaturated covalent linkages remaining by standardhydrogenation procedures, if desired. The substituted succinicanhydrides may be hydrolyzed by treatment with water or steam to thecorresponding acid and either the anhydride or the acid may be convertedto the corresponding acid halide or ester by reacting with phosphorushalide or lower alkanols.

The ethylenically unsaturated hydrocarbon reactant and the chlorinatedhydrocarbon reactant used in the preparation of the acylating agents areprincipally the high molecular weight, substantially saturated petroleumfractions and substantially saturated olefin polymers and thecorresponding chlorinated products. The polymers and chlorinatedpolymers derived from mono-olefins having from two to about thirtycarbon atoms are preferred. The especially useful polymers are thepolymers of l-monoolefins such as ethylene, propylene, l-butene,isobutene, l-hexene, l-octene, 2-methyl-l-heptene, 3-cyclohexyl-1-butene, and 2 methyl 5-propyl-1-hexene. Polymers of medial olefins,i.e., olefins in which the olefinic linkage is not at the terminalposition, likewise are useful. These are exemplified by 2-butene,3-pentene, and 4-octene.

The interpolymers of l-mono-olefins such as illustrated above with eachother and with other interpolymerizable olefinic substances such asaromatic olefins, cyclic olefins, and polyolefins, are also usefulsources of the ethylenically unsaturated reactant. Such interpolymersinclude for example, those prepared by polymerizing isobutene withstyrene, isobutene with butadiene, propene with isoprene, propene withisobutene, ethylene with piperylene, isobutene with chloroprene,isobutene with p-methylstyrene, l-hexene with 1,3-hexadiene, l-octenewith lhexene, l-heptene with l-pentene, 3-1nethyl-l-butene withl-octene, 3,3-dimethyl-l-pentene with l-hexene, isobutene with styreneand piperylene, isobutene with propylene, etc.

For reasons of oil-solubility and stability, the polymers contemplatedfor use in preparing the acylating agents of this invention should besubstantially aliphatic and substantially saturated, that is, theyshould contain at least about and perferably about on a weight basis, ofunits derived from aliphatic mono-olefins. They usually will contain nomore than about preferably no more than about 2%, olefinic linkagesbased on the total number of the carbon-to-carbon covalent linkagespresent therein.

The chlorinated hydrocarbons and ethylenically unsaturated hydrocrabonsused in the preparation of the acylating agents can have molecularweights of from about 400 up to about 100,000 or even higher. The abovedescribed polyolefins and chlorinated polyolefins having an averagemolecular weight of about 400 to about 5,000 are preferred for preparing(I). Those having molecular weights of about 700 to about 5000 areespecially prefered. Polypropylene, polyisobutylene, copolymers ofpropylene and isobutylene and their chlorinated derivatives areparticularly useful for reacting with the unsaturated acid compound toprepare suitable acylating agents. When the acylating agent has amolecular weight in excess of about 10,000, the acylated nitrogencomposition also possess viscosity index improving qualities.

In lieu of the high molecular weight hydrocarbons and chlorinatedhydrocarbons discussed above, hydrocarbons containing activating polarsubstituents which are capable of activating the hydrocarbon molecule inrespect to reaction with an ethylenically unsaturated acid reactant maybe used in the above-illustrated reactions for preparing the acylatingagents. Such polar substituents include sulfide and disulfide linkages,and nitro, mercapto, carbonyl, and formyl radicals. Examples of thesepolarsubstituted hydrocarbons include polypropene sulfide,dipolyisobutene disulfide, nitrated mineral oil, di-polyethylenesulfide, brominated polyethylene, etc.

The acylating agents may also be prepared by halogenating a highmolecular Weight hydrocarbon such as the above described olefin polymersto produce a polyhalogenated product, converting the polyhalogenatedproduct to a polynitrile, and then hydrolyzing the polynitrile. They maybe prepared by oxidation of a high molecular weight polyhydric alcoholwith potassium permanganate, nitric acid, or a similar oxidizing agent.Another method for preparing such polycarboxylic acids involves thereaction of an olefin or a polar-substituted hydrocarbon such as achloropolyisobutene with an unsaturated polycarboxylic acid such as2-pentene-1,3,5-tricarboxylic acid prepared by dehydration of citricacid. Monocarboxylic acid acylating agents may be obtained by oxidizinga monoalcohol with potassium permanganate or by reacting a halogenatedhigh molecular weight olefin polymer with a ketene. Another convenientmethod for preparing monocarboxylic acid involves the reaction ofmetallic sodium with an acetoacetic ester or a malonic ester of analkanol to form a sodium derivative of the ester and the subsequentreaction of the sodium derivative with a halogenated high molecularweight hydrocarbon such as brominated Wax or brominated polyisobutene.

The nitrogen-containing reactants, that is,

INC! filill Y-O d-z 11 (Formula A) are available through the reaction ofcommercially available products using conventional reaction techniques.Organic polycarboxylic acid acylating reagents are reacted with alkylenepolyamines characterized by the presence within the structure of thepolyamines of at least one hydroxy alkyl group to form thesenitrogen-containing reactants.

The polycarboxylic acid acylating reagents useful in preparing thenitrogen-containing reactant correspond to the general formula O HO-(J-ii-OH) 11 (Formula 13) and include the corresponding acyl halides, loweralkyl esters, and anhydrides. In this formula, R is a polyvalent organicradical whose valence equals n+1 and n is 1 to 3 provided that whenrr=1, R may also be a direct linkage between the carbon atoms. That isFormula B also repre sents oxalic acid acylating agents. R can bealiphatic, cycloaliphatic, aromatic, or heterocyclic and can besubstituted or unsubstituted. Ordinarily, R will not contain more thantwenty carbon atoms and preferably not more than ten carbon atoms. Suchacids are well-known in the art as shown by Kirk-Othmer, Encyclopedia ofChemical Technology (2nd ed.), vol. 1, pages 222-254 (1963), and otherprior art references such as Beilsteins Handbuch der Organischen Chemie,vol. II and IX, and the corresponding supplements. When R issubstituted, it can contain one or more substituents selected from theclass consisting of halo, lower alkoxy, lower alkyl mercapto, nitro,lower alkyl, and 0x0. It also may contain interrupting groups such asand the like.

Exemplary acylating reagents include phthalic acid, oxalic acid,N-phenylglycine-o-carboxylic acid, quinolinic acid, cinchomeronic acid,diphenic acid, nitrophthalic acid, isophthalic acid, terephthalic acid,mellitic acid, trimellitic acid, citric acid, tartaric acid,keto-succinic acid, bromosuccinic acid, malic acid, succinic acid,diglycolic acid, cyclohexene-4,5-dicarboxylic acid, 11131610 acid,fumaric acid, muconic acid, traumatic acid, naph-- thalic acid,2,3-pyrazine dicarboxylic acid, brassylic acid, itaconic acid,citraconic acid, mesaconic acid, acetone dicarboxylic acid, glutaconicacid, aconitic acid, triarballic acid, ethylenediaminetetracetic acid,camphoric acid, homophthalic acid, o-phenylenediacetic acid,hexahydrophthalic acid, carboxymethylthiosuccinic acid, thiodiglycolicacid, dithiodiglycolic acid, methylenebis(thioacetic acid),methylenebis(thiopropionic acid), ethylenebis(thioglycolic acid),thiophenedicarboxylic acid, tetrahydrothiophenedicarboxylic acid,thiodisuccinic acid, iminodiacetic acid, iminodipropionic acid,2,5-diethoxy-pbenzenediacetic acid, m-beuzenediacrylic acid,7,7-pphenyleneheptanoic acid, 2,2-dimethyl-l,3-cyclobutanediacetic acid,1,2-cyclobutanedipropionic acid, 1,2-cyclobutanedicarboxylic acid,1,3-cyclobutane dicarboxylic acid, and the like.

A preferred group of acids for preparing the nitrogencontainingcompounds used as intermediates in the preparation of the products ofthis invention are the dicarboxylic acids wherein the variable R is adivalent hydrocarbon radical having up to about 10 carbon atoms. Thedivalent hydrocarbon radical may be aliphatic, cycloaliphatic oraromatic, although it is preferably aliphatic.

An especially preferred group of dicarboxylic acids are those whereinthe variable R is a straight or branched chain alkylene containing up toten carbon atoms. Preferably, R separates the acid groups by at least 4carbon atoms. Illustrative of this group of acids are malonic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, and sebacic acid. As mentioned above, the derivatives ofthe foregoing acids normally employed as acylating agents can be used inlieu of the acids per se. Thus, the carboxylic acid halides, lower alkylesters (where the alkyl groups have up to 7 carbon atoms and preferably1-3 carbon atoms), and anhydrides of the foregoing acids can be used asacylating agents in preparing the nitrogen-containing reactant. Itshould also be understood that the various carboxyl groups present inthe carboxylic acids need not be present in the same form, that is, onemay be a carboxyl group per se and another can be a carboalkoxy group orcarboxylic acid halide group. Obviously, mixtures of these variousacylating agents can also be employed in 7 the preparation of thenitrogen-containing reactant. Such mixtures could include two or more ofany of the foregoing polycarboxylic acids or their halides, esters, oranhydrides, such as a combination of succinic acid anhydride and adipicacid.

The amines which are reacted with the polycarboxylic acids to form thenitrogen-containing reactant are alkylene polyamines having up to tenamino nitrogens present in their structure and having at least onehydroxy alkyl present in the polyamine molecule. The presence of thishydroxy alkyl group is an important characteristic of the amines used toprepare the present additives. The emulsion resistance and emulsionbreaking capabilities of the additives seems to depend, in part atleast, on the presence of at least one group in the nitrogen-containingreactant. These amines can be represented by the following generalformula:

RIRIN RII NRI) RII NRIRI (Formula C) wherein m, R and R are as definedhereinbefore with the further proviso that at least one R per polyaminemolecule is -H. A preferred class of polyamines are those where the Rvariables are either H or -ROH where R" and r are as defined aboveproviding at least one R is H- and at least one is /I An especiallypreferred group of amines are those of the type described above wherethe variable R is alkyl ene of up to six carbon atoms and particularlyethylene or propylene, one R is and the remaining R variables are -Hs.

The most preferred polyamine reactants are those falling within theclass represented by the formula that is, where m of Formula C is 0. Inthis most preferred group, those amines where one R vanable ls and theremaining three R variables are hydrogen are particularly useful. Inthis most preferred class of alkylene diamines, the variable R generallywill contain from two to six carbon atoms and desirably will be ethyleneor propylene. The R variables need not be identical within a givenpolyamine. The N-(hydroxy-lower alkyl)- alkylene diamines (particularlyethylene diamines) such as N-(fl-hydroxyethyl)-ethylene diamine,N-(fl-hydroxypropyl) -ethylene diamine,N-(B-hydroxy-[i-methylpropyl)-ethylenediamine constitute especiallyuseful amines within this most preferred class.

Other specific exemplary polyamines corresponding to 'Formula C includeN-(3-hydroxypropyl)-trimethylene diamine,N-(4-hydroxybutyl)-tetran1ethylene diamine, N-(fl-hydroxyethyl)-hexamethylene diamine, N-(4-hydroxybutyl)-ethylenediamine, N-(3-hydroxyhexyl)-ethylenediamine, N-(2 tolyl 3hydroxypropyl)-trimethylene diamine,N-(2-phenyl-3-hydroxyheptyl)-ethylene diamine, mono-hydroxy propylsubstituted diethylene triamines, dihydroxypropyl-substitutedtetracthylene pentamines,

8 and the like. Other polyamines falling within the class of preferredamines are disclosed in the prior art such as in US. Pat. 3,018,173which is hereby incorporated by reference.

These amines are available commercially or can be synthesized accordingto known techniques. See for example, US. Pats. 3,018,173 and 3,282,836and M. S. Malinovskii, Okisi Olefinov I Ikh Pruizvodnye (1961),translated by L. Balig as Epoxides and Their Derivatives (1965)published by Daniel Davey & Co., Inc. N.Y. particularly pages 222-223 ofthe translation. Basically, these amines can be prepared by reacting analkylene polyamine such as ethylene diamine, diethylene triamine,triethylene tetramine, tetraethylene pentamine, pentaethylene hex amine,propylene diamine, dipropylene triamine, tripropylene tetramine,trimethylene diamine, tetramethylene diamine, pentamethylene diamine,hexamethylene diamine, di(trimethylene)triamine, and the like with atleast one epoxide. The term epoxide as used herein means alkylene oxidesor mono-aryl substituted alkylene oxides having from two to eight carbonatoms such as ethylene oxide, propylene oxide, epichyorohydrin, butyleneoxides, styrene oxide or mixtures thereof. The 1,2-a1kylene oxides suchas ethylene and propylene oxide are preferred. The alkylene polyamineand the alkylene oxide should be reacted in a molar ratio of alkylenepolyamine to alkylene oxide of about 1:1 to about 1:10. Normally,however, the number of moles of alkylene oxide reacted with each mole ofalkylene polyamine will not exceed that number which is one less thanthe number of amino groups in the polyamine. For example, the number ofmoles of alkylene oxide to be reacted with tetraethylene pentaminenormally would not exceed four; with dipropylene triamine, two, etc. Amole ratio of about 1:1 results in particularly useful intermediates.

As will be apparent to those skilled in the art, when the epoxidecontains an aryl substituent on the alkylene group, the reaction productwill also retain this substituent. For example, styrene oxide andethylene diamine react to produce N-(fl-hydroxy-B-phenylethyl)-ethylene.(See Balig, above.) Usually, if present, there will be only one sucharyl substituent per alkylene oxide and it will be a phenyl orsubstituted phenyl substituent such as lower alkyl substituted phenyl,lower alkoxy substituted phenyl, nitro phenyl, and the like. Similarly,the alkylene group of the epoxide may contain other groups such as haloand alkoxy. Again these groups will become substituents on thepolyamine-epoxide reaction products.

Suitable epoxides include glycidol, epichlorohydrin, epibromohydrin,ethylether of glycidol, amyl ether of glycidol, phenyl glycidol,1,2-epoxypentane, 1,2-epoxyhexane, 2,3-epoxypentane, 1,2-epoxyoctane,1,2,5,6-diepoxyhexane, 2,4,4-trimethyl-2,3-epoxypentane, styrene oxide,and the like.

Other methods for preparing hydroxyhydrocarbyl-substituted polyaminesare known in the prior art. For example, a hydroxyhydrocarbyl halide canbe reacted with a polyamine having reactive NH groups to prepareN(-hydroxycarbyl)-substituted polyamines. Thus, the polyamines usefulfor reacting with epoxides can also be reacted with such compounds asIIO CH CH Cl, IIOCII CILCHOHCH CI, CH CHOHCH CH CI according to knownprocedures to prepare suitable amines.

The variable R in the amines and the Alkylene-Cl ene, phenylene, and thelike. The hydrocarbylene groups may contain nonhydrocarbon substituentssuch as lower alkoxy, lower alkylmercapto, oxo, nitro, amino, etc., andsuch polar-substituted hydrocarbylene groups are contemplated asequivalent to hydrocarbylene groups per se. However, such substituentsdo not appear to contribute to any substantial improvement in the finalproducts. Thus, R normally will be divalent hydrocarbon and, preferably,alkylene of up to ten carbon atoms.

As suggested above, it is contemplated that some of the R variables onthe polyamines and the nitrogencontaining reactants, that is, (II), maybe hydrocarbyl of up to ten carbon atoms. This term is intended todescribe monovalent aliphatic, cycloaliphatic, araliphatic, aryl, etc.hydrocarbon radicals which are free from ethylenic or acetylenicunsaturation. Again, the corresponding substituted radicals containingsuch substituents as lower alkoxy, lower alkylmercapto, nitro, loweralkyl, etc., are deemed to be equivalent to the unsubstitutedhydrocarbon radical. Such substituted hydrocarbyl groups arecontemplated as being within the scope of this invention herein.Generally, when R is a hydrocarbyl radical, it will be a monovalenthydrocarbon such a cyclohexyl, 3- ethylcyclohexyl, cyclopentyl, phenyl,tolyl, benzyl, phenethyl, propyl, heptyl, etc. Preferably, if a Rvariable is other than H or it will be lower alkyl of up to seven carbonatoms. As stated before, R is preferably H if not The polycarboxylicacid acylating reagents (Formula B) are reacted with the R -OH-snbstituted polyamines in amounts such that there is at least aboutone equivalent of the carboxylic acid acylating agent for each mole ofpolyamine reactant. Usually, not more than one mole of carboxylic acidacylating reagent will be used for each mole of polyamine reactant. Forpurposes of this invention, the equivalent weight of the carboxylic acidacylating reagent is its molecular weight divided by the number ofcarboxylic acid groups or acylating functional derivatives thereofpresent in the molecule. Thus, ethylenediaminetetracetic acid has fourequivalents per mole while succinic acid and adipic acid each have twoequivalent per mole. Preferably, the acylating reagent and polyaminewill be reacted in a ratio of about one equivalent to one mole.

The carboxylic acid acylating reagents and the polyamines can be reactedat temperatures of about 50 C. up to the decomposition temperature ofthe reactants or the resulting product. Normally, however, there is noadvantage in exceeding temperatures of about 300 C. Preferably,temperatures of at least 100 C. to about 260 C. will be employed.

If desired, the reaction can be conducted in the presence of asubstantially inert diluent such as the liquid hydrocarbons andhalohydrocarbons, ethers, and the like. Specific inert liquid diluentssuitable for the use in this process include mineral oils, naphthas,benzenes, toluene, xylenes, chlorobenzenes, heptane, hexane, pentane,cycloheptane, cyclohexane, chlorohexane, butyl ether, isobutyl ether,amyl ether, isoamyl ether, methyl amyl ether, ethyl amyl ether, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, and the like, andmixtures thereof. Inert atmosphere (e.g., nitrogen, helium, etc.) andsuperatmospheric or subatmospheric pressures can be used.

As is apparent to those skilled in the art, both the carboxylic acidacylating reagents and the polyamines have a plurality of reactivefunctional groups. Accordingly, a

diverse group of reaction products is possible and the specific natureof the product will depend on the particular carboxylic acid andpolyamines utilized, the ratio of the reactants, the reactiontemperature, and the like. Thus, the carboxylic acid acylating reagentscan react with amino hydrogens to form amides, imides, or amidines. Onthe other hand, the carboxyl groups can react with the hydroxyl hydrogento form esters. Likewise, the carboxylic acid acylating reagent mayretain some unreacted carboxyl functions. The products of the reactionbetween the carboxylic acid acylating agent and the polyamine arerepresented by general Formula A above.

While any nitrogen-containing compounds corresponding to Formula A aresuitable reactants including mixtures thereof, it is preferred that thepolycarboxylic acid acylating agent and the polyamine be reacted underconditions whereby no (or substantially no) unreacted carboxyl groupsremains. This is readily accomplished simply by conducting the reactionat a sufficiently high temperature C. or higher) and/or for a sufficientlength of time to permit complete reaction. Obviously there will have tobe at least about one equivalent of HO or HN= or combination thereofpresent in the reaction mixture for each equivalent of acylating agentin order to provide for the reaction of all the carboxyl groups orequivalent acylating function derivatives thereof.

When the polyamine used to prepare the nitrogen-containing reactant is amember of the most preferred class of amines represented by the generalformula:

/H LEN-Alkylene-N Alkylene-O H (Formula E) the acylating agent is analiphatic dicarboxylic acid acylating agent corresponding to Formula B,and the amine and acid are reacted in a molar ratio of about 2:1 thenthe nitrogen-containing reaction product consists predominantly ofcompounds of the formula:

Alkylene- O H (Formula F) N N Alkylene C-R- 0 Alkylene l Alkylene-OHAlkylene-OH (Formula G) or mixtures thereof. For example, whenN-(B-hydroxyethyl)-ethylene diamine and adipic acid are reacted asdiscussed below, the product would consist predominantly of compoundscorresponding to Formula F or G or mixtures thereof where the alkylenegroups are ethylene and the R variable is -(CH An alternative processfor preparing suitable nitrogencontaining reactants involves firstreacting at least one polycarboxylic acid acylating reagent representedby Formula B with at least one polyamine of the formula:

where R" and m are as defined above and R is hydrogen or hydrocarbyl ofup to ten carbon atoms. At least two R s are H and, desirably all ofthem are H. Preferably, R" will be alkylene having two to six carbonatoms therein, the ethylene polyamines and propylene polyaminescorresponding to Formula H being particularly preferred. The acylatingreagent and the alkylene polyamine should be reacted at temperatures offrom about 50 C. up to about the decomposition temperature of thereactants or reaction products. However, there is usually no advantagein employing temperatures in excess of 300 C. Temperatures of at leastabout 100 C. are preferred with temperatures of at least about 200 C.being especially preferred. This process is discussed in more detailhereinbelow.

The acylating reagent and the polyamine are reacted in amounts such thatthere is at least one equivalent of acylating agent for each mole ofpolyamine but the ratio of acylating reagent to polyamine should be suchthat there is an average of at least one unreacted =NH group remainingper molecule of the reaction product for subsequent reaction with anepoxide. Accordingly, the maximum amount of the acylating reagent whichshould be employed in the reactant is that amount such that the ratio ofequivalents of acylating reagent to polyamine is not greater than X-l :Xwhere X is the number of equivalents of polyamine present in thereaction mixture. For purposes of this invention, the equivalent weightof a polyamine is its molecular weight divided by the number of NHgroups present therein. Thus, the equivalent weight of ethylene diamineis one-half of its molecular weight, the equivalent weight oftetraethylene pentamine is one-fifth of its molecular weight; and soforth. The preferred ratio of reactant is about one equivalent ofacylating reagent for each mole of polyamine. The products of thisreaction are amides, imides, amidines, or mixtures thereof. As in thepreparation of the nitrogen-containing intermediate according to theother general process discussed above, the process should be conductedunder conditions which result in no (or substantially no) unreactedcarboxyl groups.

This first reaction product is then further reacted with at least oneepoxide of the type described hereinabove. The amount of epoxideemployed in this subsequent reaction should be such that there is atleast about one mole of epoxide for each mole of alkylene polyamine usedin preparing the first reaction product. Up to ten moles of epoxide canbe used for each mole of alkylene polyamine.

As with the first method of preparing the nitrogen-containing reactant,the processes can be conducted in the presence of inert diluents such asthose enumerated hereinbefore. Likewise, inert atmospheres as well assub-atmospheric and super-atmospheric pressures can be employed. Theepoxides can be reacted with the acylated nitrogen reaction products attemperatures from about C. up to the decomposition temperature of thereactant or the reaction product. There is little advantage in exceedingtemperatures of about 300 C. Reaction temperatures of about 40 to about150 C. are usually vary satisfactory.

It is critical to this invention that the nitrogen-containing reactant(II) be first prepared and subsequently reacted with the acylating agent(I). If the polyamines represented by Formula C are first reacted withthe acylating agent (I) and thereafter with the acylating reagentsrepresented by Formula B, different reaction products are produced.Similarly, if polyamines corresponding to Formula C wherein all the Rvariables are H are first reacted with the acylating reagents, then thatreaction product is reacted with (I), and this second reaction productthen reacted with an epoxide, the final reaction product is differentfrom the additives of this invention. Moreover, the simultaneousreaction of all these starting materials also results in reactionproducts which are different from the present additives.

In preparing the additives of this invention, at least one monoorpolycarboxylic acid acylating agent characterized by the presence withinits structure of at least about thirty aliphatic carbon atoms exclusiveof carboxyl carbon atoms is reacted with at least onenitrogen-containing reactant of the type represented by Formula A above.The acylating agent and the nitrogen-containing reactant are reacted inamounts such that there is at least one equivalent of the acylatingagent for each mole of the nitrogen-containing reactant. As with theacylating reagents discussed above, the equivalent weight of the monoorpolycarboxylic acid acylating agent is its average molecular weightdivided by the number of carboxyl functions present. Thus, analkenyl-substituted methacrylic acid has one equivalent per mole whilean alkenyl-substituted succinic acid or anhydride would have twoequivalents per mole as mentioned before. As the nitrogen-containingproduct can be a mixture of various products corresponding to Formula A,it would be difficult to determine with absolute certainty the number ofmoles of nitrogen-containing product actually present in the reactionmixture. Accordingly, for purposes of this invention, it is assumed thatthe number of moles of nitrogen-containing product is equivalent to thenumber of moles of acylating reagent which are reacted in thepreparation of the nitrogen-containing product. For example, if thenitrogen-containing reaction product is prepared by reacting one mole ofadipic acid with two moles of N-(ti-hydroxyethyD-ethylene diamine, it isassumed that the reaction product contains one mole ofnitrogen-containing reactant.

The acylating agent and the nitrogen-containing reactant can be reactedat temperatures ranging from about C. up to the decompositiontemperature of the reactants and of the final product. Ordinarily,however, the temperature will not exceed 300 C. Preferably, temperaturesof at least C. up to about 260 C. will be used to facilitate theformation of predominantly ester, amide, imide, or amidine groups inlieu of amine salt groups in the additive.

The reaction can be conducted in the presence of inert diluents of thetype described hereinbefore if desired. Mineral oils are particularlyuseful diluents if the resulting products are to be used as additivesfor lubricating oils including two-cycle engine lubricants. Morevolatile diluents may be advantageous where the product is to beincorporated in fuel compositions such as gasoline, diesel fuel, furnacefuel oils, and the like. Of course, where the diluent is sufficientlyvolatile, it can be easily removed by conventional distillationtechniques, if desired.

The reaction can be conducted in an inert atmosphere such as nitrogen orhelium if desired. Moreover, subatmospheric and super-atmosphericpressures can be employed as desired.

It has also been found that the dispersant-capabilities and/or theemulsion sludge resistant properties as well as other characteristics ofthe additives of this invention may be enhanced by post-treatment of thereaction products of (I) and (II) with at least one member selected fromthe group consisting lower aliphatic acids, lower aliphatic aldehydes,and epoxides. Mixtures of one or more of these post-treating materialsare also useful. The post-treatment comprises contacting the reactionproducts of (I )and (II) with one of the above enumerated materials at atemperature of about 25 C. up to about 300 C. and preferably from about50 C. up to about 200 C. The post-treating materials will be employed inan amount ranging from about 0.01% to about 20% by weight based on thetotal weight of (I) and (II) used in the preparation of the reactionproducts. Usually, 0.1% to 10.0% of the post-treating materials will beemployed. Any unreacted post-treating material can be removed, ifdesired, by conventional techniques such as low pressure distillation,etc.

The lower aliphatic acids which can be used in the post treatmentprocess include principally the lower aliphatic monoand dicarboxylicacid acylating agents containing from one to seven carbon atoms as wellas their acyl halides, lower alkyl esters, and their anhydrides. Suchacids are illustrated by formic acid, acetic acid, propionic acid,butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, oxalicacid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelicacid, maliec acid, fumarc acid, gluconic acid, acetyl chloride, ethylpropionate, succinic anhydride, glacial acetic acid, and the like. The

13 14 lower alkanoic acids per se are preferred with formic acidanhydride and 629 parts of mineral oil are mixed and being especiallypreferred. heated at 185195 C. for five hours While blowing with Thealdehydes contemplated for use in the post-treatnitrogen at a rate ofabout 12 standard cubic feet per ment process are the aliphaticaldehydes containing up to hour. The reaction mass is then filtered at125 C., the

seven canbon atoms such as formaldehyde, acetaldehyde, filtrate being anoil solution of the desired additive of propionaldehyde, butyraldehyde,valeraldehyde, hexaldethis invention.

hyde, heptaldehyde, acrolein, and the like. The lower alkyl EXAMPLE 3monoaldehydes o A mixture consisting of 930 parts of N-(hydroxyethyl)- 1ethylene diamine and 651 parts of adipic acid are heated (wet 31ky1 H)under reflux conditions to 190 C. with nitrogen blowing are preferredwith formaldehyde or its equivalents such over a 1.5 hour period. Thismixture is maintained at 185- as par-aldehyde and formalin beingespecially preferred. 195 C. untl 230 cc. of water are evolved. Theresulting The epoxide suitable for use in the post-treatmentprocreaction mixture is then stripped to 200 C. at 13 mm. ess are thosedescribed hereinabove with regard to the (Hg). preparation of thenitrogen-containing intermediate. The Thereafter, 425 parts of the aboveproduced reaction 1,2-alkylene oxides, especially ethylene and propyleneproduct which consists predominantly of products conoxide are preferredfor use in the post-treatment process. forming to the general Formulas Fand G, 1540 parts of The present invention is further illustrated by thefolpolyisobutenyl-substituted succinic anhydride having an lowingexamples. As used in the present specification and average molecularweight of 1030, and 1292 parts of claims, percentages and parts refer topercent by mineral oil are charged to a reaction flask fitted with aweight and parts by weight unless otherwise indicated. reflux condenser.This mixture is then heated to 185 C. EXAMPLE 1 over a l-hour periodwhile blowing with nitrogen and is thereafter held at 185l99 C. for 3.25hours during To a reaction flask fitted with a reflux condenser therewhich time the nitrogen blowing is continued. The reaction is added 150parts of ethylene diamine, then 110 parts mass is then cooled to 130 C.and filtered producing of ethylene oxide are blown through the ethylenediamine 2975 grams of a oil solution of the desired additive. during a1.75-hour period at a rate of about l-1.5 stand- Following the generalprocedure of Example 3, the ard cubic feet per hour while maintainingthe temperature materials enumerated in Table I below are reacted in theof the reaction mixture at 95 l45 C. To the result- 30 indicatedquantities to produce additional additives of ing mixture is then added146 parts of adipic acid and the type contemplated by the presentinvention.

TABLE I Example Carboxylic acid Molar ratio N o. Amine reactant (A)acylating reagent (B) Acylating agent (0) (A) (B): (C)

4 N -(3-hydroxypropyl)propylene diamine Adipic acid Polypropyiegfe (mol.wt. 800)-substituted snc- 2. 1:11

cinic anhy i e. 5 N-(Z-hydropmpyl) e hy1ene diamme Malomc acldPolyisobutylene (mol. wt. 450)-substituted 2:1;0.5

succinic anhydride. 6 N-(4-hydroxyoctyl)ethylene diamine Gluta.r1c acidPolyisobutylene (moi. wt. 1,200)-snbstitnted 2.2:1z0. 75

succinic anhydride. 7 N-(3-hydroxyhepty1)-tetramethyiene diamine.Sebac1c acid Polyisobutylene (mol. wt. 900)-substituted 2;1:2

I acrylic acid. 8 N-(Z-hydroxyethyl)-ethylene dlamme Tercphthalic acidIsobutylene-propylene copolymer (80% by 2:1:1

Wt. isobntylene units; (mol. Wt. 1,500)- substituted succinic anhydride)9 N-(B-hydroxypentyl)-trnnethylene diamine (1 Adipic acid (0.5 mole)mole Polypropylene (mol. Wt. 600) substituted suc-N-((12-hyldroxyheptyl)-tetramethy1ene diamine Azelaic acid (0.5 mole)citric acid. 211:1

mo e 10 N-(2-hydroxy-2-phenylethyl)-ethylene diamine. Diglycolic acidPolyisobutylene (moi. wt. 3,000)-substituted 211:1

succinic anhydride. 11 N-(2-to1yi-3-hydroxypropyl)propylene diamine.Imlnodiacetic acid Same as Example 5 211:1 12 N-(2-hydroxypropyl)ethylene diamine 1,4-pgenyienediacetic Same as Example7 2:1:0. 1

this mixture is then heated at 150-160 C. for 4 hours Following thegeneral procedure of Example 3, it is while blowing with nltrogen.During this time 42 millipossible to prepare other additives of the typecontemliters of water are evolved and trapped. Thereafter, 1057 platedby the present invention simply by replacing all parts ofpolyisobutenyl-substituted succinic anhydride or part of the materialsidentified in Table I as (A)(C) having an average molecular Weight ofabout 1057 is with other amines, acylating reagents, and acylatingagents introduced into the mixture over a 1.5 hour period While of thetype discussed more fully hereinabove.

maintaining a temperature of 150-163 C. The mass is While the foregoingexamples are directed to a prethen heated to 200 C. with nitrogenblowing over a 1.25 ferred subgenus of the present invention, that is,addihour period and held for 1.5 hours at ZOO-210 C. While tivesprepared from N-(hydroxyalkyD-alkylene diamines, continuing the nitrogenblowing. This mixture is then additives can also be readily prepared byusing polyamines cooled to 165 C. and 940 parts of mineral oil are addedcorresponding to Formula C other than the hydroxyalkylproducing amineral oil solution of the desired product. ene diamines. The followingexample illustrates the prep- This solution is then heated to 150 C. andfiltered, the aration of other polyamines which are suitable forsynfiltrate being an oil solution of the desired additive. 6r thesizingthe nitrogen-containing reactants used to pre- 0 EXAMPLE 2 pare theadditives of this invention. A mixture of 260 parts of'N-(hydroxyethyD-ethylene EXAMPLE 13 diamine and 260 parts of xylene isheated to C. There- (A) Tetraethylene pentamine (1 mole) is charged toafter 146 parts of adipic acid are added to the mixture a reaction fiaskfitted with a Dry Ice reflux condenser over a 5 minute-period whilemaintaining a temperature and 1.5 moles of ethylene oxide are slowlyblown through of 80120 C. This mixture is heated under reflux at theamine While maintaining a temperature of 50 60 C. for twenty-four hours.Thereafter, the solvent is C. for 4 hours.

stripped from the reaction product by heating to 180 C. (B) A mixture ofethylene polyamine consisting of at 12 millimeters (Hg) pressure. Then,209 parts of the two moles of diethylene triamine and 2 moles oftriethresidue, 755 parts of polyisobutenyl-substituted succinic 75 ylenetetramine is reacted with 1.25 moles each of eth- 15 ylene oxide andpropylene oxide following the procedure of (A) above.

(C) Following the procedure of (A) above, 1 mole of tetraethylenepentamine is reacted with 1.75 moles of epichlorohydrin.

(D) Two hundred and thirty-three parts of a commercially availablemixture of ethylene polyamine sold under the name Polyamine D by UnionCarbide Corporation is reacted with 174 parts of propylene oxidefollowing the general procedure of (A) above.

(E) Following the procedure of (A), 1 mole of diethylene triamine isreacted with 1 mole of styrene oxide.

(F) Following the procedure of (A), 1 mole of triethylene tetramine isreacted with styrene oxide.

By substituting equimolar amounts of the reaction products of the abovepolyamines and epoxides for all or part of (A) in Examples 112 above,additional additives of the type falling within the scope of the presentinvention are readily prepared.

EXAMPLE 14 (A) To a reaction mixture comprising 240 parts of ethylenediamine and 450 parts of xylene, there is slowly added over a period ofone hour 146 parts of adipic acid while maintaining a temperature ofabout 75 C. Thereafter, the reaction mixture is refluxed for 8 hours ata temperature of about 235-245 C. while nitrogen gas is blown throughthe mass. Then 200 parts of mineral oil are added with stirring. The oilcontaining mixture is then stripped at reduced pressure to removeunreacted amine and xylene. Then 90 parts of ethylene oxide are slowlyintroduced (evenly over a two hour period) into the residue which is ina reaction flask fitted with a Dry Icecooled reflux condenser whilemaintaining a temperature of about 90 C. After all the ethylene oxidehas been added, the mass is maintained under reflux conditions for anadditional two hours at 140-145 C. Subsequently, 300 parts of mineraloil and 1100 parts of polyisobutenylsuccinic anhydride (average N.W.about 1100) are added and this mixture is heated at about 200 C. forfour hours while nitrogen is blown through the mass at about 2.0standard cubic feet per hour. The reaction mixture is filtered, thefiltrate being an oil-solution of the desired additive.

(B) The process of (A) is repeated substituting an equimolar amount ofdiethylene triamine and propylene oxide for the ethylene diamine andethylene oxide.

(C) The procedure of (A) is repeated substituting an equimolar amount oftetraethylene pentamine and propylene oxide for the ethylene diamine andethylene oxide, respectively.

(D) Part (A) is repeated using 240 parts of propylene oxide in lieu ofthe 90 parts of ethylene oxide.

(B) Part (A) is repeated substituting 800 parts of the acylating agentof Example 4 for the polyisobutenyl succinic anhydride.

(F) Part (C) is repeated using 205 parts of sebacic acid in lieu of theadipic acid.

(G) Part (B) is repeated using 2000 parts of the acylating agent ofExample 7 in lieu of the polyisobutenyl succinic anhydride.

Still further additives of the type contemplated by the presentinvention can be prepared by substituting other alkanedioic acids,alkylene polyamines, epoxides, or acylating agents for those used inExample 14. For example, equimolar amounts of the acylating reagents andacylating agents described in Table I can be substituted for those usedin each part of Example 14. Similarly, equivalent amounts of otheralkylene polyamines and alkylene oxides of the type describedhereinabove may be used in lieu of those of that example.

In practicing the procedure of Example 14, a stoichiometric excess ofthe polyamine reactant should be used. There should be at least aboutone and 0ne-half moles of polyamine for each equivalent ofpolycarboxylic acid acylating reagent and preferably there will be atleast about two moles. There is little advantage in using more than fourmoles of polyamine for each equivalent of acylating reagent. Of course,if the acylating reagent is an acyl chloride, allowances should be madefor the amount of amine which will react with the hydrogen halideproduced. The excess amine is used to prevent the production of largeamounts of long-chain polyamides. After completion of the reaction,i.e., when substantially all the carboxyl functions have reacted withamino groups to form amide, imide, or amidine linkages, the excess aminecan be removed by conventional techniques, e.g., distillation at reducedpressure, etc.

While temperatures of about 50-300 C. are useful for the process ofExample 14, it is desirable to employ temperatures of at least about 150C. Further, it is preferred that conditions conducive to the formationof amidine linkages be employed in the reaction between the acylatingreagent and the alkylene polyamine. Thus, temperatures of about 200-300"C. are preferred for this step of the reaction with temperatures ofabout 2l0260 C. being especially suitable for this step.

The polyamine reactants used in the process illustrated by Example 14will preferably be characterized by at least one radical of the formulaH N-alkylene NH. Alkylene polyamines corresponding to Formulae C and Dwhere each R is H and the alkylene dicarboxylic acids of Formula B whereR is alkylene are preferred for the first step of the process.

The following examples illustrate preferred embodiments of the inventionas it relates to the additives prepared by post-treatment withaldehydes, carboxylic acids, and epoxides as discussed above.

EXAMPLE 15 (A) Into 1000 parts of a filtrate produced in accordance withthe procedure of Example 3, there is introduced slowly under refluxconditions 60 parts of propylene oxide over a 2-hour period whilemaintaining a temperature of about -100 C. The resulting mixture isheated under reflux an additional two hours. The resulting reactionproduct is an oil-solution of an epoxide post-treated additive of thisinvention.

(B) The procedure of (A) is repeated using 40 parts of ethylene oxideand the reaction product of Example 4.

(C) The procedure of (A) is repeated using parts of styrene oxide and areaction temperature of about 200 C.

By substituting 0.01% to 20% by weight of other epoxides (based on thetotal weight of additive product exclusive of diluent) for those inExample 15(A)-(C), other epoxide post-treated products can be prepared.Similarly, other non-post-treated additives can be substituted for thatof Examples 3 and 4.

EXAMPLE 16 (A) To a mixture consisting of 1000 parts of the filtrate ofExample 3 there are added over a 0.5-hour period 50 parts of formic acidwhile maintaining a temperature of about 100-105 C. at refluxconditions. The resulting mixture is maintained under these conditionsfor about 3.5 hours with nitrogen blowing. Thereafter, the mass isheated to C. for one hour at reduced pressure. The residue is an oilsolution of the desired formic acid treated product.

(B) Part (A) is repeated using 20 parts of glacial acetic acetic and 20parts of formic acid in lieu of this 50 parts of formic acid.

(C) Part (A) is repeated using 5 parts of formic acid.

EXAMPLE 17 (A) A mixture of 1000 parts of a filtrate produced accordingto Example 3 and 50 parts of a 37% aqueous formalin are heated underreflux conditions at about 95-l05 C. for four hours. Thereafter, thereaction mixture is blown with nitrogen for an hour while maintaining atemperature of about 150 C. without reflux conditions. The resultingproduct is an oil solution of the desired posttreated additive.

(B) Procedure (A) is repeated using 30 parts of nbutyraldehyde in lieuof the formalin.

The general procedures of Examples 16 and 17 can be repeated using otheracids, aldehydes, and non-posttreated additives described in detailhereinbefore to prepare additional post-treated additives of the typecontemplated by this invention.

As mentioned above, the additives of this invention are useful in bothlubricant and fuel compositions. They can be elfectively employed in avariety of lubricant compositions based on diverse oils of lubricatingviscosity such as a natural or synthetic lubricating oil, or suitablemixtures thereof. The lubricating compositions contemplated includeprincipally crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines including automobile andtruck engines, two-cycle engine lubricants, aviation piston engines,marine and railroad diesel engines, and the like. However, automatictransmission fluids, transaxle lubricants, gear lubricants,metal-working lubricants, hydraulic fluids, and other lubricating oiland grease compositions can benefit from the incorporation of thepresent additives.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as solvent-refined or acid-refined mineral lubricatingoils of the paraffinic, naphthenic, or mixed paraflinic-naphthenictypes. Oils of lubricating viscosity derived from coal or shale are alsouseful base oils. Synthetic lubricating oils include hydrocarbon oilsand halo-substituted hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes, etc.);alkyl benzenes (e.g., dodecylbenzenes, tetradecylbenzene,dinonylbenzenes, dis-(Z-ethylhexyl)benzenes, etc.); polyphenyls (e.g.,biphenyls, terphenyls, etc.); and the like. Alkylene oxide polymers andinterpolymers and derivatives thereof where the terminal hydroxyl groupshave been modified by esterification, etherification, etc., constituteanother class of known synthetic lubricating oils. These are exemplifiedby the oils prepared through polymerization of ethylene oxide orpropylene oxide, the al-kyl and aryl ethers of these polyoxyalkylenepolymers, e.g., methylpolyisopropylene glycol ether having an averagemolecular weight of 1000, diphenyl ether of polyethylene glycol having amolecular weight of 500-1000, diethyl ether of polypropylene glycolhaving a molecular weight of 1000-1500, etc.) or monoand polycarboxylicesters thereof, for example, the acetic acid esters, mixed C -C fattyacid esters, or the C oxo acid diester of tetraethylene glycol. Anothersuitable class of synthetic lubricating oils comprises the esters ofdicarboxylic acids (e.g., phthalic acid, succinic acid, maleic acid,azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid,linoleic acid dimer, etc.) with a variety of alcohols (e.g., butylalcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol,pentaerythritol, etc.). Specific examples of these esters includedibutyl adipate, di(2- ethylhexyl) sebacate, di-n-hexyl fumarate,dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctylphthalate, didecyl phthalate, dieicosyl sebacate, the Z-ethylhexyldiester of linoleic acid dimer, the complex ester formed by reacting onemole of sebacic acid with two moles of tetraethylene glycol and twomoles of Z-ethyl-hexanoic acid, and the like. Silicon-based oils such asthe polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils andsilicate oils comprise another useful class of synthetic lubricants(e.g., tetraethyl-silicate, tetraisopropyl-silicate, tetra- 2-ethylhexyl-silicate, tetra- 4-methyl-2-tetraethyl silicate, tetra-(p-tert-butylphenyl) -silicate, hexyl- 4-methyl-2-pentoxy) disiloxane,poly(methyl)-siloxanes, poly (methylphenyl)-siloxanes, etc.). Othersynthetic lubricating oils include liquid esters ofphosphorus-containing 18 acids (e.g., tricresyl phosphate, trioctylphosphate, diethyl ester of decane phosphonic acid, etc.), polymerictetrahydrofurans, and the like.

The lubricating compositions contemplated by this invention are thosecontaining a major amount of a lubricating oil of the type describedhereinabove and a minor amount of the additives of this invention. Theamount of additives employed, of course, is dependent upon theparticular environment in which the lubricant is to be used and theother components of the lubricating composition, if any. However, thelubricating compositions will usually contain from about 0.01% to about30% by weight of the present additives. Crankcase lubricants forgasolinefueled automobile and truck engines will generally contain fromabout 0.1% to about 10% by weight of the additives and usually fromabout 0.5% to about 5% by weight. However, diesel engines, particularlyrailroad diesels and marine diesels, may contain up to 30% or more byweight of these additives. Similarly, gear lubricants may contain asmuch as 10% by weight or more of the additives.

The additives may also be used in lubricating compositions for two-cycleengines, that is, lubricating compositions which are added directly tothe fuel which is to be burned in these engines. Lubricatingcompositions for twocycle engines which comprise this additive willcontain from about to 99% of a lubricating oil and from about 1 to 20%of one or more of the additives of this invention. Ordinarily, however,the additive will not exceed about 10% by weight of the two-cyclelubricant composition.

It is also contemplated that other conventional additives will bepresent in the lubricating compositions of this invention. Suchadditives include detergents of the ash-containing type, other ashlessdispersants, viscosity index improving agents, pour point depressants,anti-foam agents, extreme pressure agents. rust inhibiting agents, andother oxidation and corrosion inhibitors. Suitable ashless dispersantsfor use in combination with the additives of this invention areexemplified by those disclosed in the patents incorporated hereinabovefor their disclosure of suitable monoand polycarboxylic acid acylatingagents for preparing the additives of this invention. Generally, theseare the amides, imides, and esters, of alkylene polyamine or polyhydricalcohols.

The ash-containing detergents are exemplified by the oil-soluble neutraland basic salts of alkali or alkaline earth metals with sulfonic acids,carboxylic acids, or organic phosphorus acids. The latter arecharacterized by at least one direct carbon-to-phosphorus linkage suchas those prepared by the treatment of an olefin polymer (e.g.polyisobutylene having an average molecular weight of about 1000) with aphosphorizing agent such as phosphorus trichloride, phosphorusheptasulfide, phosphorus pentasulfide, phosphorus trichloride andsulfur, white phosphorus and a sulfur halide, or phosphorothioicchloride. The most commonly used salts of such acids are the sodium,potassium, lithium, calcium, magnesium, strontium, and barium salts.

The term basic salt is used to designate those metal salts wherein themetal is present in stoichiometrically larger amounts than the organicacid radical. The commonly employed methods for preparing the basicsalts involves heating a mineral oil solution of an acid with astoichiometric excess of a metal neutralizing agent such as the metaloxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature ofat least about 50 C. and filtering the resulting mass. The use of apromoter in the neutralization step to aid the incorporation of a largeexcess of metal is known. Examples of compounds useful as promotersinclude phenolic substances such as phenol, naphthol, alkylphenols,thiophenols, sulfurized alkylphenols, and condensation products offormaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, Cellosolve, Carbitol, ethylene glycol,

stearyl alcohol, and cyclohexyl alcohol; amines such as aniline,phenylene diamine, phenothiazine, and dodecyl amine. Illustrativeash-containing detergents and processes for their preparation arediscussed in detail in such US. patents as 3,027,325; 3,312,618;3,377,281.

Extreme pressure agents, corrosion inhibitors, oxidation inhibitors andthe like such as are contemplated for use in the compositions of thepresent invention are also well-known in the art and include, forexample, chlorinated aliphatic hydrocarbons such as chlorinated wax;organic sulfides and polysulfides such as benzyl disulfides,bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized sperm oil,sulfurized methyl ester of maleic acid, sulfurized alkyl phenol,sulfurized dipentene, and sulfurized turpene; phosphosulfurizedhydrocarbons such as the reaction product of a phosphorus sulfide withturpentine or methyloleate and the phosphorus esters includingprincipally dihydrocarbon and trihydrocarbon phosphates such as dibutylphosphate, diheptyl phosphite, dicyclohexyl phosphite, pentylphenylphosphite, dipentyl phenyl phosphite, tridecyl phosphite, distearylphosphite, dimethyl naphthyl phosphite, oleyl- 4-pentylphenyl phosphite,polypropylene (molecular weight-500)-substituted phenyl phosphite,diisobutyl substituted phenyl phosphite; metal thiocarbamate such aszinc dioctyl-thiocarbamate and barium heptylphenyl dithiocarbamate;Group II metal phosphorodithioates such as zincdicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, bariumdi(heptylphenyl) phosphorodithioate, cadmium dinonylphosphorodithioate,and zinc salts of a phosphorodithioic acid produced by the reaction ofphosphorus pentasulfide with an equal molar mixture of isopropyl alcoholand n-hexyl alcohol.

The lubricating compositions of this invention can contain the metalcontaining detergents in amounts up to about 20% by weight. In someapplications such as lubricants for marine diesel engines, thelubricating compositions may contain as much as 30% by weight of a metaldetergent additive. The other components in the composition will bepresent in amounts in which such components are ordinarily used, thatis, in amounts of about 0.001% to about 10% by weight.

The additives of this invention are also useful as components in fuelswherein they function as sludge dispersants, emulsion breakers andretardants, anti-screen clogging agents. In liquid fuels used ininternal combustion engines, they also serve to promote the generalcleanliness of the fuel system such as fuel pumps, carburetors, and thelike and to reduce the deposition of deposits in the exhaust system.

The fuels contemplated for use with the additives of this invention aregenerally the petroleum distillate fuels including diesel fuels, furnacefuels, jet fuels, aviation fuels and include fuel oils, kerosene, andgasolines. In fuels, the additives will be used in amounts such thatthey comprise from about 0.000l% to about by weight of the fuelcomposition and preferably from about 0.001% to about 1% by weight ofthe total fuel composition.

The fuel compositions of this invention may contain other conventionaladditives such as alkyl or alkenyl lead anti-knocking agents e.g.,tetraethyl lead, tetramethyl lead, tetravinyl lead; corrosioninhibitors, anti-oxidants, antistatic agents, lead octane appreciators,lead scavengers, anti-icing agents, smoke suppressants, and the like.

The following compositions are illustrative of lubricants and fuelscontemplated by the present invention.

Composition A SAE- W- mineral lubricating oil containing 0.75% of anadditive produced according to Example 2.

Composition B SAE3O mineral lubricating oil containing 2% of the productof Example 3, 0.075% of phosphorus as zinc dioctylphosphordithioate, and5% of the barium salt of an acidic composition prepared by the reactionof 1000 parts of polyisobutene having the molecular weight of 60,000

with parts of phosphorus pentasulfide at 200 C. and

hydrolyzing the product with steam at C.

Composition C SAE10 mineral lubricating oil containing 1.5% of theproduct of Example 7, 0.075% of phosphorus as the adduct obtained byheating zinc di-nonylphosphorodithioate with 0.25 mole of 1,2-hexeneoxide at 120 C., 2% of a sulfurized methyl ester of tall oil acid havinga sulfur content of 15%, 6% of a polyisobutene viscosity index improvingagent, 0.005% of a poly-(alkylmethacrylate) anti-foam agent, and 0.5 oflard oil.

Composition D SAE-lO mineral lubricating oil containing 2% of theproduct of Example 7, 0.07% of phosphorus as zincdioctylphosphorodithioate, 2% of barium detergent prepared byneutralizing with barium hydroxide the hydrolyzed reaction product ofpolypropylene (molecular weight-2000) with one mole of phosphoruspentasulfide and one mole of sulfur, 3% of a barium sulfonate detergentprepared by carbonating a mineral oil solution of mahogany acid and a500% stoichiometrically excess amount of barium hydroxide in thepresence of heptylphenol as a promoter at a 180 C., 3% of a supplementalashless detergent prepared by copolymerizing a mixture of 95% ofdecyl-methacrylate and 5% of diethylamino ethylacrylate.

Composition E A synthetic lubricant which is the diphenyl ether ofpolyethylene glycol having a molecular weight of about 1000 and 0.5% ofthe additive produced according to Example 3.

Composition F Gasoline containing 0.05% of the additive producedaccording to Example 3.

Composition G Kerosene containing 0.15% of the additive producedaccording to Example 7.

Composition H Diesel fuel containing 0.008% of the additive producedaccording to Example 4.

Composition I Gasoline containing 0.2% of the product of Example 2.

The emulsion sludge resistance of the additives of this invention isdemonstrated by the following engine test results of lubricatingcompositions differing only in the nature of the ashless dispersantpresent. Composition X is a mineral lubricating oil compositioncontaining two prior art ashless dispersants. One is a reaction productof (l) polyisobutenyl succinic acid anhydride and (2) the reactionproduct of polyethylene polyamines and acrylonitrile as described inExample 3 of US. Pat. No. 3,278,550. The other is the reaction productof (1) polyisobutenyl succinic acid anhydride and (2) polyethylenepolyamines of the type in Example 5 of US. Pat. No. 3,172,892. Each ispresent in composition in an amount of about 1.5 by weight. CompositionY is the same as Composition X but the two ashless dispersants arereplaced with about 3% by weight of the additive produced according toExample 3.

Each composition is employed in test engines which are operated underidentical conditions. At the end of each day of operation the emulsionsludge resistance of the lubricant is ascertained by the amount ofemulsion sludge formed on the rocker arm covers. A rating of 10represents no sludge deposit. The results achieved with Composition Xand Y are tabulated below.

TABLE II Emulsion sludge rating 1 Days of engine operation Composition XComposition Ratings are the averages of two engine tests of eachcomposition.

As seen by the foregoing results, the additive of Example 3 results inless sludge after seven days than is present after either the first orsecond day with the prior art dispersants. Yet the additive of Example 3is also an effective ashless dispersant. These results also demonstrateanother advantage of the additives of this invention, particularly thoseprepared from N-(hydroxyalkyl)-alkylene diamines. Their emulsion sludgeresistance appears to improve somewhat with engine operation and theycontinue to function efiectively for a long period of time.

What is claimed is:

1. An oil-soluble acylated nitrogen composition produced by the processcomprising reacting at a temperature of from about 75 C. up to thedecomposition temperature:

(I) at least one substantially saturated aliphatic monoor polycarboxylicacylating agent characterized by the presence of at least about thirtyaliphatic carbon atoms exclusive of carboxyl carbon atoms and averagemolecular weight of from about 400 to about 100,000, with (II) at leastone nitrogen-containing reactant, said reactant having been produced byreacting at a temperature of about 50 C. up to the decompositiontemperature (a) a polycarboxylic acid acylating reagent selected fromthe class consisting of the formula and their corresponding acylhalides, lower alkyl esters, and anhydrides where R is a polyvalentorganic radical which does not contain more than twenty carbon atoms andwhose valence equals 11 plus 1, n is a whole number of 1 to 3, with theproviso that R may also be a direct linkage between the carbon atoms,with (b) a polyamine of the formula I I II ILRH NRIRI R R \R NR where Ris H, hydrocarbyl of up to ten carbon atoms, or

where r is a whole number of l to but at least one R per polyaminemolecule is and at least one R per polyamine molecule is H, and R ishydrocarbylene of up to ten carbon atoms, (a) and (b) having beenreacted in a ratio of at least about one equivalent of (a) up to aboutone mole of (a) for each mole of (b), where (I) and (II) are reacted inamounts such that there is at least one equivalent of the acylatingagent for each mole of nitrogen containing reactant.

2. A composition according to claim 1 wherein (I) and (II) as well as(a) and (b) are reacted at temperatures of at least 100 C. up to about260 C.

3. A composition according to claim 2 wherein said polycarboxylic acidacylating reagent (a) is a dicarboxylic acid acylating reagent selectedfrom the class consisting 22 of the acids per se and their correspondingacyl halides, lower alkyl esters, and anhydrides where R is a divalenthydrocarbon radical having up to about 10 carbon atoms. 4. A compositionaccording to claim 3 wherein said polyamine (b) is further characterizedin that the R variables are either H or providing one R is H and atleast one R is 5. A composition according to claim 4 wherein R is adivalent aliphatic hydrocarbon radical.

6. A composition according to claim 5 where said polyamine (b) isfurther characterized in that all R groups are alkylene of up to sixcarbon atoms, one R is where one R is and the remaining R groups are H.

9. A composition according to claim 8 Where the di carboxylic acidacylating reagent (a) is further characterized in that R separates theacid groups by at least four carbon atoms.

10. A composition according to claim 9 wherein all the R" groups areethylene or propylene.

11. A composition according to claim 2 wherein (I) has been prepared byreacting at a temperature of about -300 C. (i) an ethylenicallyunsaturated carboxylic acid reactant of the formula Rfl-COOH-h, or itscorresponding acyl halide, ester, or anhydride, where n is one or twoand R is characterized by the presence of at least one ethylenic linkagein an otfi-POSitiOII with respect to at least one carboxyl function, thetotal number of carbon atoms in R tCOOH-h, not exceeding ten, with (ii)substantially saturated, substantially aliphatic polyolefins orchlorinated polyolefins having average molecular weights of about 400 toabout 5000.

12. A composition according to claim 4 wherein (I) has been prepared byreacting at a temperature of about 100-300 C. a member selected from thegroup consisting (i) of acrylic acid, methacrylic acid, maleic acid,maleic anhydride, furnaric acid, itaconic acid, itaconic anhydride,citraconic acid, citraconic anhydride, mesaconic acid, glutaconic acid,chloromaleic acid, aconitic acid, crotonic acid, methylcrotonic acid,sorbic acid, 3-hexenoic acid, and 10-decenoic acid with (ii)substantially saturated, substantially aliphatic polyolefins orchlorinated polyolefins having average molecular weights or about 400 toabout 5000.

13. A composition according to claim 7 where (I) has been prepared byreacting at a temperature of about 100-300 C. (i) a member selected fromthe class consisting of a-fi-ethylenically unsaturated dicarboxylicacids and the corresponding anhydrides having up to six carbon atomswith (ii) a member selected from the group consisting of polypropylene,polyisobutylene, and their chlorinated derivatives having molecularweights of about 700 to about 5000.

14. A composition according to claim 9 where (I) has been prepared byreacting at a temperature of about 100-300 C. (i) a member selected fromthe class consisting of ot-fi-ethylenically unsaturated dicarboxylicacids and the corresponding anhydrides having up to six carbon atomswith (ii) a member selected from the group consisting of polypropylene,polyisobutylene, and their chlorinated derivatives having molecularweights of about 700 to about 5000.

15. A composition according to claim 2 wherein the reaction product of(I) and (II) has been post-treated at a temperature of about 25 C. up toabout 300 C. with at least one member selected from the group consistingof lower aliphatic acids and the corresponding acyl halides, lower alkylesters, and anhydrides, lower aliphatic aldehydes, and alkylene oxidesand mono-aryl substituted alkylene oxides, said oxides having two toeight carbon atoms in amounts such that the post-treating materialscomprise from about 0.01% to about 20% by weight of the total weight of(I) and (II).

16. A composition according to claim 4 wherein the reaction product of(I) and (II) has been post-treated at a temperature of from about 50 C.up to about 200 C. with at least one member selected from the groupconsisting of lower aliphatic monoand dicarboxylic acids and theircorresponding acyl halides, lower alkyl esters, and anhydrides, loweralkyl monoaldehydes, 1-2 alkylene oxides, said alkylene oxides havingtwo to eight carbon atoms, in such amounts that the post-treatingmaterials comprise from about 0.1% to about by weight of the totalweight of (I) and (II).

17. A composition according to claim 7 wherein the reaction product of(I) and (II) has been post-treated at a temperature of from about 50 C.up to about 200 C. with at least one member selected from the groupconsisting of lower aliphatic monoand dicarboxylic acids and theircorresponding acyl halides, lower alkyl esters, and anhydrides, loweralkyl monoaldehydes, l-2 alkylene oxides, said alkylene oxides havingtwo to eight carbon atoms, in such amounts that the post-treatingmaterials comprise from about 0.1% to about 10% by weight of the totalweight of (I) and (II).

18. A composition according to claim 11 wherein the reaction product of(I) and (II) has been post-treated at a temperature of from about 50 C.up to about 200 C. with at least one member selected from the groupconsisting of lower aliphatic monoand dicarboxylic acids and theircorresponding acyl halides, lower alkyl esters, and anhydrides, loweralkyl monoaldehydes, 1-2 alkylene oxides, said alkylene oxides havingtwo to eight carbon atoms, in such amounts that the post-treatingmaterials comprise from about 0.1% to about 10% by weight of the totalweight of (I) and (II).

19. A composition according to claim 12 wherein the reaction product of(I) and (II) has been post-treated at a temperature of from about 50 C.up to about 200 C. with at least one member selected from the groupconsisting of lower aliphatic monoand dicarboxylic acids and theircorresponding acyl halides, lower alkyl esters, and anhydrides, loweralkyl monoaldehydes, 1-2 alkylene oxides, said alkylene oxides havingtwo to eight carbon atoms, in such amounts that the post-treatingmaterials comprise from about 0.1% to about 10% by weight of the totalweight of (I) and (II).

20. A composition according to claim 13 wherein the reaction product of(I) and (II) has been post-treated at a temperature of from about 50 C.up to about 200 C. with at least one member selected from the groupconsisting of lower aliphatic monoand dicarboxylic acids and theircorresponding acyl halides, lower alkyl esters, and anhydrides, loweralkyl monoaldehydes, 12 alkylene oxides, said alkylene oxides having twoto eight carbon atoms, in such amounts that the post-treating materialscomprise from about 0.1% to about 10% by weight of the total weight of(I) and (-II).

21. A composition according to claim 14 wherein the reaction product of(I) and (II) has been post-treated at a temperature of from about 50 C.up to about 200 C. with at least one member selected from the groupconsisting of lower aliphatic monoand dicarboxylic acids and theircorresponding acyl halides, lower alkyl esters, and anhydrides, loweralkyl monoaldehydes, l-2 alkylene oxides, said alkylene oxides havingtwo to eight carbon atoms, in such amounts that the post-treatingmaterials comprise from about 0.1 %to about 10% by weight of the total'weight of (I) and (II).

22. An oil-soluble acylated nitrogen composition produced by the processcomprising reacting at a temperature of at least about 50 C. up to aboutthe decomposition temperature at least one alkylene polyamine of theformula R R N O O Hatattafi) and their corresponding acyl halides, loweralkyl esters, and anhydrides where R is a polyvalent organic radicalwhich does not contain more than twenty carbon atoms and whose valenceequals n+1, n is a whole number of 1 to 3, with the proviso that R mayalso be a direct linkage between the carbon atoms, in a molar ratio ofacylating reagent to polyamine of at least one equivalent of acylatingreagent per mole of polyamine to form a first reaction composition;reacting this first reaction composition at a temperature of from about25 C. up to the decomposition temperature with at least one epoxideselected from the class consisting of alkylene oxides andmono-aryl-substituted alkylene oxides in an amount such that the molarratio of epoxide to the polyamine used in preparing the first reactioncomposition is about 1:1 to about 10:1 to form a second reactioncomposition; and thereafter reacting the second reaction composition ata temperature of from about 75 C. up to the decomposition temperaturewith at least one substantially saturated aliphatic monoorpolycarboxylic acid acylating agent characterized by the presence withinits structure of at least about thirty aliphatic carbon atoms exclusiveof the carboxyl carbon atoms and average molecular weight of from about400 to about 100,000, the amount of high molecular weight carboxylicacid being such that there is at least one equivalent of said at leastone substantially saturated aliphatic monoor polycarboxylic acidacylating agent for each mole of polyamine employed in the preparationof the first reaction composition.

23. An oil-soluble acylated nitrogen composition according to claim 22wherein: said at least one polyamine and said acylating reagent arereacted at a temperature of at least about 0.; said at least oneacylating reagent corresponds to Formula B where R is a divalenthydrocarbon radical of up to about ten carbon atoms and n is 1 and thecorresponding lower alkyl esters and anhydrides; said first reactionmixture and said at least one epoxide are reacted at a temperature ofabout 40 C. to about C.; said at least one substantially saturatedaliphatic monoor polycarboxylic acid acylating agent is selected fromthe high molecular weight monoand polycarboxylic acids and anhydrides;and said second reaction composition and said at least one substantiallysaturated aliphatic monoor polycarboxylic acid acylating agent arereacted at a temperature of at least 100 C. up to about 260 C.

24. An oil-soluble acylated nitrogen composition according to claim 23wherein: said at least one epoxide is 1,2-alkylene oxide; said R groupsare H; R separates the carboxylic acid groups by at least four carbonatoms; and said at least one substantially saturated aliphatic monoorpolycarboxylic acid acylating agent is selected from those prepared byreacting at a temperature of about 100-300 C. (i) an ethylenicallyunsaturated carboxylic acid reactant of the formula R (COOH) or itscorresponding acyl halide, ester, or anhydride, where n is one or twoand R is characterized by the presence of at least one ethylenic linkagein an a,/3-position with respect to at least one carboxyl function, thetotal number of carbon atoms in RflCOOI-I) not exceeding ten, with (ii)substantially saturated, substantially aliphatic polyolefins andchlorinated polyolefins having average molecular weights of about 400 toabout 5000.

25. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adispersant amount of an oil-soluble acylated nitrogen compositionaccording to claim 1.

26. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adispersant amount of an oil-soluble acylated nitrogen compositionaccording to claim 5.

27. A. lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adispersant amount of an oil-soluble acylated nitrogen compositionaccording to claim 8.

28. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adispersant amount of an oil-soluble acylated nitrogen compositionaccording to claim 15.

29. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adispersant amount of an oil-soluble acylated nitrogen compositionaccording to claim 21.

30. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adispersant amount of an oil-soluble acylated nitrogen compositionaccording to claim 22.

References Cited UNITED STATES PATENTS 3,219,666 11/1965 Norman et a1.25251.5 A 3,287,271 11/1966 Stuart et al. 25251.5 A 3,373,111 3/1968LeSuer et a1. 252-51.5 A 3,401,118 9/1968 Benoit 25251.5 A

DANIEL E. WYMAN, Primary Examiner W. J. SHINE, Assistant Examiner US.Cl. XJR.

4463, 71; 260268 PL, 268 H, 3265 F, 326.5 FM

' UNITED STATES PATENT OFFICE CERTIFICATE OF CGRRECTION Patent ,No. 3 3,9 I Dated December 28, 1971 Inventor(s) Jerry L. Musser et'al It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below: 7

At column 26, line 3, that is Claim27, line 5,

"claim 8" should. be -'--Claim 11--.

Signed and sealed this 29th day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER JR. Q ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents USCOMM-DC 60376-P69 U 5 GOVERNMENT PRINTING OFFICE: I9690-366-334 FORM PO-105O (10-69)

